KR100478865B1 - Method of removing inorganic contamination by chemical derivitization and extraction - Google Patents
Method of removing inorganic contamination by chemical derivitization and extraction Download PDFInfo
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- KR100478865B1 KR100478865B1 KR1019970034640A KR19970034640A KR100478865B1 KR 100478865 B1 KR100478865 B1 KR 100478865B1 KR 1019970034640 A KR1019970034640 A KR 1019970034640A KR 19970034640 A KR19970034640 A KR 19970034640A KR 100478865 B1 KR100478865 B1 KR 100478865B1
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000126 substance Substances 0.000 title claims description 11
- 238000011109 contamination Methods 0.000 title description 3
- 238000000605 extraction Methods 0.000 title 1
- 239000000356 contaminant Substances 0.000 claims abstract description 74
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000012530 fluid Substances 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- 239000002738 chelating agent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
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- 238000004140 cleaning Methods 0.000 description 10
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- 150000002739 metals Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000003398 denaturant Substances 0.000 description 6
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003508 chemical denaturation Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0021—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by liquid gases or supercritical fluids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
-
- C11D2111/22—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S134/00—Cleaning and liquid contact with solids
- Y10S134/902—Semiconductor wafer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S438/00—Semiconductor device manufacturing: process
- Y10S438/902—Capping layer
Abstract
본 발명의 실시예는 실질적으로 반도체 기판의 표면으로부터 무기 오염물을 제거하는 방법으로서, 이 방법은 무기 오염물을 적어도 하나의 변환제와 반응시켜 무기 오염물을 변환시키는 단계, 및 변환된 무기 오염물에 제1 초임계 유체(양호하게는, 초임계 CO2)에 포함된 적어도 하나의 용매제를 가하여 변환된 무기 오염물을 제거하는 단계를 포함하며, 변환된 무기 오염물은 무기 오염물보다 용매제에 대한 용해도가 높다.An embodiment of the present invention is a method for substantially removing inorganic contaminants from a surface of a semiconductor substrate, the method comprising reacting inorganic contaminants with at least one converting agent to convert inorganic contaminants, and converting the inorganic contaminants into a first Adding at least one solvent contained in the supercritical fluid (preferably, supercritical CO 2 ) to remove the converted inorganic contaminants, wherein the converted inorganic contaminants are more soluble in solvent than the inorganic contaminants. .
Description
본 발명은 반도체 디바이스의 제조 및 처리에 관한 것으로, 특히 반도체 구조체의 표면의 무기 오염물을 제거하는 것에 관한 것이다.TECHNICAL FIELD The present invention relates to the manufacture and processing of semiconductor devices, and more particularly to the removal of inorganic contaminants on the surface of semiconductor structures.
예를 들어, 집적 회로 및 액정 디스플레이의 제조시, 기판 및 후속 반도체층의 오염은 많은 문제점들을 야기하므로 가능한 한 감소되어야 한다. 그러한 오염의 예로는 잔여 입자, 유기물 및 금속이 있다. 게다가, 오염물은 반도체층의 표면 상에 위치될 수도 있고 반도체층과 다른 층(예를 들어, 산화물 층) 사이에 위치될 수도 있다. 통상적으로, 반도체 디바이스의 제조에는 습식 공정이 이용되고 있다. 습식 세정 공정은 일련의 입자 제거 및 금속 제거 공정으로 이루어지며, 이들 공정 사이에 세척 공정이 수행되며 마지막으로 건조 공정이 수행된다. 건조는 통상적으로 웨이퍼를 회전시켜 웨이퍼 상의 액체가 원심력에 의해 제거되게 하거나, 웨이퍼의 표면 상에 응축되어 물과 치환하는 고온 이소프로필 알콜 증기의 클라우드로부터 웨이퍼를 들어 올림으로써 수행된다.For example, in the manufacture of integrated circuits and liquid crystal displays, contamination of the substrate and subsequent semiconductor layers causes many problems and should be reduced as much as possible. Examples of such contaminations are residual particles, organics and metals. In addition, contaminants may be located on the surface of the semiconductor layer and may be located between the semiconductor layer and another layer (eg, an oxide layer). Usually, the wet process is used for manufacture of a semiconductor device. The wet cleaning process consists of a series of particle removal and metal removal processes, with a cleaning process between these processes and finally a drying process. Drying is typically accomplished by rotating the wafer to allow the liquid on the wafer to be removed by centrifugal force, or by lifting the wafer from a cloud of hot isopropyl alcohol vapor that condenses on the surface of the wafer and replaces with water.
이러한 유형의 습식 세정 공정은 특별히 심각한 결점을 갖는데, 특히 이러한 유형의 대부분의 금속 제거 공정(통상, 강산성 혼합물을 이용함)은 웨이퍼의 표면에 입자들을 첨가하며, 입자 제거 공정(통상, 염기성/산화제 혼합물을 이용함)은 웨이퍼의 표면에 금속을 첨가한다. 게다가, 대부분의 습식 세정 공정은 다음과 같은 문제점, 즉 전자 등급의 습식 화학 물질을 획득하는 비용, 습식 세정 공정에서 사용되는 가성(caustic) 화학 물질의 처리 비용, 트랜치처럼 높은 종횡비 특성에 대해 습식 화학 세정을 제한하거나 방지하는 액체 표면 장력; 및 (반도체 처리시 보다 자주 사용되는) 모든 건조 처리와의 부조화와 같은 문제점을 갖는다. 따라서, 금속 제거 공정 후에 입자 제거 공정을 실시하면 잔여 금속이 발생되고, 반대로 입자 제거 공정 후에 금속 제거 공정을 실시하면 입자는 보다 적어지지만 최종 세척 시 금속에 의해 오염될 수 있다.This type of wet cleaning process has a particularly serious drawback, in particular most metal removal processes of this type (typically with strong acid mixtures) add particles to the surface of the wafer and the particle removal process (usually basic / oxidant mixtures). Is added to the surface of the wafer. In addition, most wet cleaning processes offer the following challenges: the cost of obtaining electronic grade wet chemicals, the cost of treating caustic chemicals used in wet cleaning processes, and high aspect ratio characteristics such as trenches. Liquid surface tension to limit or prevent cleaning; And incompatibility with all drying treatments (more frequently used in semiconductor processing). Therefore, when the particle removal process is performed after the metal removal process, residual metal is generated. On the contrary, when the metal removal process is performed after the particle removal process, the particles become smaller, but may be contaminated by the metal during the final cleaning.
최근, 초임계 유체[(supercritical fluid), 즉 초임계 CO2]가 큰 주목을 받아왔다. 커피의 카페인 제거 및 리넨(linen)/파인(fine) 의류의 드라이 크리닝을 포함하는 분야에서 특히 그렇다. 게다가, 반도체 웨이퍼로부터 유기 오염물을 제거하는 데에 초임계 CO2가 사용될 수 있다. "International Journal of Environmentally Conscious Design & Manufacturing" 제 2권 p83(1993)의 "supercritical carbon dioxide is best applied to the removal of organic compounds with mid-to-low volatilities"를 참조하라. 그러나, 초임계 CO2는 일반적으로 반도체 웨이퍼로부터 무기 오염물(즉, 금속)을 제거하는 데에는 비효율적인 것으로 여겨진다.Recently, supercritical fluids, ie supercritical CO 2, have received great attention. This is especially true in the field of caffeine removal of coffee and dry cleaning of linen / fine garments. In addition, supercritical CO 2 may be used to remove organic contaminants from semiconductor wafers. See “supercritical carbon dioxide is best applied to the removal of organic compounds with mid-to-low volatilities” in International Journal of Environmentally Conscious Design & Manufacturing,
또 다른 분야와 관련하여, 연구자들은 식물에 초임계 CO2를 가하고 킬레이트제(chelating agent)로 금속을 중화하여 식물로부터 금속을 제거하는 방법을 발견하였다. 엘리자벳 케이. 윌슨(Elizabeth K. Wilson)의 "Toxic Metals Extracted with Supercritical Carbon Dioxide", C&EN 27(1996. 4. 15) 및 미국 특허 제5,356,538호를 참조하라. 그러나, 이러한 문헌은, "양으로 하전된 중금속 이온을 용해(solvate)시키는 데에 있어서, 비극성 초임계 CO2는 거의 쓸모없다"고 언급하고 있다. 그러나, 연구자들은 금속이 킬레이트제에 의해 중화되면 용해될 수 있으며, 더욱이 킬레이트제가 플루오르화되면 용해도가 매우 증가한다는 것을 발견하였다. 그러나, 이러한 방식에는 여러가지 문제점이 존재한다. 첫째로, 하전되지 않은 금속을 제거하기가 어렵다. 둘째로, 플루오르화되지 않은 킬레이트제는 고가이다. 셋째로, 플루오르화된 킬레이트제의 대량 합성은 많은 비용이 든다. 넷째로, 플루오르화된 킬레이트제 및 플루오르화되지 않은 킬레이트제는 독성이 강하고, 정제하여 처리하는데 많은 비용이 든다. 다섯째로, 플루오르화된 킬레이트제에 의해 쉽게 용해되는 금속의 범위가 제한된다. 여섯째로, 상기 문헌의 방법을 이용하는 경우 킬레이트화되지 않은 금속이 하부 반도체 기판으로 확산하면 피해가 극심하다.In another field, the researchers found a way to remove metals from plants by adding supercritical CO 2 to the plants and neutralizing the metals with chelating agents. Elizabeth K. See " Toxic Metals Extracted with Supercritical Carbon Dioxide ", C & EN 27 (April 15, 1996) and US Pat. No. 5,356,538 to Wilson K. Wilson. However, this document states that "non-polar supercritical CO 2 is almost useless in solubilizing positively charged heavy metal ions." However, the researchers found that metals could be dissolved if they were neutralized by the chelating agent and, furthermore, solubility increased greatly when the chelating agent was fluorinated. However, there are several problems with this approach. First, it is difficult to remove the uncharged metal. Second, the fluorinated chelating agent is expensive. Third, mass synthesis of fluorinated chelating agents is expensive. Fourthly, fluorinated chelating agents and non-fluorinated chelating agents are highly toxic and expensive to purify and process. Fifth, the range of metals that are easily dissolved by fluorinated chelating agents is limited. Sixth, the damage of the unchelated metal diffuses into the lower semiconductor substrate is severe when using the method of the above document.
그러므로, 본 발명의 목적은 반도체 웨이퍼로부터 금속 오염물을 제거하는 방법을 제공하는 것이다. 본 발명의 또 다른 목적은 반도체 웨이퍼로부터 무기 오염물을 제거하는 방법을 제공하는 것이다.Therefore, it is an object of the present invention to provide a method for removing metal contaminants from a semiconductor wafer. It is another object of the present invention to provide a method for removing inorganic contaminants from a semiconductor wafer.
요약하면, 본 발명의 일 실시예는 이온성 및 중성의 경질 및 중질 무기(금속) 물질의 화학 변성에 수반되는 문제점을 해결하고, 이러한 이온성 및 중성의 경질 및 중질 무기(금속) 물질을 종래 염가의 고순도 무독성 용매에 노출시킴으로써 용해되도록 하는 방법이다. 본 발명의 방법은 자연히 존재하는 산화물(반도체 기판 상부에 존재함)의 표면 상의 금속 무기 오염물을 화학적으로 변화시키는 공정을 포함한다. 이것은 양호하게는, 매우 넓은 범위의 변성제/화학 물질을 이용하여 달성하는 것이 바람직하며, 초임계 유체(양호하게는, CO2)에 노출시키기 전 또는 노출시키는 동안 금속의 변화가 발생될 수도 있다. 그 후, 화학적으로 변화된 금속을 초임계 CO2 유체에 배합한 통상의 용매에 노출시킨다. 마지막으로, 종래 방식으로 용해되고 화학적으로 변화된 금속을 초임계 CO2 용매 내에서 제거한다. 본 발명의 주요 특징은 무기 오염물이 사전에 화학적인 변화가 없었다면 초임계 CO2 유체에 용해되지 않으며 화학적으로 변화된 무기 오염물은 그 화학 변화 공정과 동시에 용매에 의해 제거된다는 것이다.In summary, one embodiment of the present invention solves the problems associated with chemical denaturation of ionic and neutral hard and heavy inorganic (metal) materials, and prioritizes such ionic and neutral hard and heavy inorganic (metal) materials. It is a method to dissolve by exposure to a cheap, high purity non-toxic solvent. The method of the present invention includes a process of chemically changing a metal inorganic contaminant on the surface of a naturally present oxide (present on top of a semiconductor substrate). This is preferably achieved using a very wide range of denaturing agents / chemicals, where metal changes may occur before or during exposure to the supercritical fluid (preferably CO 2 ). The chemically changed metal is then exposed to conventional solvents blended into the supercritical CO 2 fluid. Finally, the metal dissolved and chemically changed in a conventional manner is removed in a supercritical CO 2 solvent. The main feature of the present invention is that the inorganic contaminants are not dissolved in the supercritical CO 2 fluid unless there has been a prior chemical change and the chemically changed inorganic contaminants are removed by the solvent at the same time as the chemical change process.
본 발명의 실시예는 실질적으로 반도체 기판의 표면으로부터 무기 오염물을 제거하는 방법으로서, 이 방법은, 상기 무기 오염물을 적어도 하나의 변환제(conversion agent)와 반응시켜 상기 무기 오염물을 변환시키는 단계; 및 상기 변환된 무기 오염물을 제1 초임계 유체(supercritical fluid)에 함유된 적어도 하나의 용매제(solvent agent)에 가하여, 상기 변환된 무기 오염물을 제거하는 단계를 포함하며, 상기 변환된 무기 오염물은 상기 무기 오염물보다 용매제에 대한 용해도가 높은 것을 특징으로 한다. 양호하게는, 상기 변환제는 산, 염기, 킬레이트제, 리간드제, 할로겐 함유제, 및 이들의 임의의 조합으로 이루어진 그룹에서 선택된다. 상기 무기 오염물은 상기 기판 상에 존재하는 자생 산화물의 실질적인 표면에 위치하며, 이는 금속 오염물로 구성될 수도 있다. 상기 변환제는 제2 초임계 유체 내에 함유될 수도 있으며, 상기 제2 초임계 유체는 초임계 CO2 인 것이 바람직하다. 상기 무기 오염물을 적어도 하나의 변환제와 반응시키는 단계 및 상기 변환된 무기 오염물을 적어도 하나의 용매제에 가하여 상기 변환된 무기 오염물을 제거하는 단계는 동시에 또는 순차적으로 수행될 수 있다. 양호하게는, 상기 용매제는 극성 가스(polar gas), 비극성 가스(nonpolar gas), 극성 초임계 유체, 비극성 초임계 유체, 극성 물질(polar species), 비극성 물질(nonpolar species), 계면 활성제, 세정제, 양성 물질 또는 킬레이트제로 이루어진 그룹에서 선택된다.An embodiment of the present invention is a method for substantially removing inorganic contaminants from a surface of a semiconductor substrate, the method comprising: converting the inorganic contaminants by reacting the inorganic contaminants with at least one conversion agent; And adding the converted inorganic contaminants to at least one solvent agent contained in a first supercritical fluid to remove the converted inorganic contaminants. It is characterized by higher solubility in solvents than the inorganic contaminants. Preferably, the converting agent is selected from the group consisting of an acid, a base, a chelating agent, a ligand, a halogen containing agent, and any combination thereof. The inorganic contaminants are located on a substantial surface of the native oxide present on the substrate, which may be composed of metal contaminants. The converting agent may be contained in a second supercritical fluid, and the second supercritical fluid is preferably supercritical CO 2 . Reacting the inorganic contaminants with at least one converter and removing the converted inorganic contaminants by adding the converted inorganic contaminants to the at least one solvent may be performed simultaneously or sequentially. Preferably, the solvent is a polar gas, nonpolar gas, polar supercritical fluid, nonpolar supercritical fluid, polar species, nonpolar species, surfactants, detergents , A positive substance or a chelating agent.
본 발명의 또 다른 실시예는 실질적으로 반도체 기판의 표면으로부터 금속 오염물을 제거하는 방법으로서, 상기 방법은, 상기 금속 오염물을 제1 초임계 CO2 유체에 함유된 적어도 하나의 변환제와 반응시켜 상기 금속 오염물을 변환시키는 단계; 및 상기 변환된 무기 오염물을 제2 초임계 CO2 유체에 함유된 적어도 하나의 용매제에 가하여, 상기 변환된 무기 오염물을 제거하는 단계를 포함하며, 상기 변환된 금속 오염물은 상기 금속 오염물보다 용매제에 대한 용해도가 높은 것을 특징으로 한다. 상기 금속 오염물을 적어도 하나의 변환제와 반응시키는 단계 및 상기 변환된 무기 오염물을 적어도 하나의 용매제에 가하여 상기 변환된 금속 오염물을 제거하는 단계는 동시에 또는 순차적으로 수행될 수 있다.Another embodiment of the present invention is a method for substantially removing metal contaminants from a surface of a semiconductor substrate, the method comprising reacting the metal contaminants with at least one converter contained in a first supercritical CO 2 fluid. Converting metal contaminants; And adding the converted inorganic contaminant to at least one solvent contained in a second supercritical CO 2 fluid to remove the converted inorganic contaminant, wherein the converted metal contaminant is a solvent than the metal contaminant. It is characterized by high solubility in. Reacting the metal contaminant with at least one converting agent and removing the converted metal contaminant by adding the converted inorganic contaminant to at least one solvent may be performed simultaneously or sequentially.
이제, 첨부 도면을 참조하여 본 발명을 보다 상세히 설명하기로 한다.The present invention will now be described in more detail with reference to the accompanying drawings.
도 1은 본 발명의 방법을 수행하는 데에 사용될 수 있는 처리 시스템을 도시한다. 세정될 샘플(무기 오염물이 존재하는 반도체 웨이퍼)이 용기(16) 내에 보유되어 있다. 초임계 유체(양호하게는, CO2 가스)는, 밸브(32)를 포함하는 도관(30)에 의해 접속된 가스통(28)으로부터, 대략 32℃ 이상의 온도에서 대략 70 내지 75 기압 이상으로 기체에 압력을 가하여 초임계 유체를 생성하는 가압 유닛(34; pressurization unit)에 공급된다. 초임계 유체(SCF)는, [밸브(1 및 3)가 개방되고 밸브(2)가 폐쇄되는 한] 밸브(36) 및 도관(38)을 통해 고체, 액체 또는 기체 변성제를 보유하는 통(12)으로 이동한다. 이하, 가능한 변성제를 나열하기로 한다. SCF를 변성제에 통과시키면 변성제가 SCF와 결합한다. 변성제와 결합된 SCF는 통(12)을 떠나 용기(16)로 유입된다. SCF 혼합물 및 무기 오염물이 도입되어 무기 오염물을 변성시킨다.1 illustrates a processing system that can be used to perform the method of the present invention. A sample to be cleaned (a semiconductor wafer with inorganic contaminants) is held in the
변성제에 의한 반도체 샘플 상의 무기 오염물의 변성 이후 또는 동시에, SCF는 밸브(36) 및 도관(38)을 통해 고체, 액체 또는 기체 용매제를 보유하는 가스통(14)으로 이동한다. 이것은 폐쇄 밸브(1, 3 및 5) 및 개방 밸브(2, 4 및 6)에 의해 달성된다. 용매제에 SCF를 통과시키면 용매제가 SCF에 섞여 들어간다. 용매제와 배합된 SCF는 통(12)을 나와 용기(16)로 유입된다. SCF 혼합물 및 변성된 무기 오염물이 도입되어 샘플(양호하게는, 반도체 웨이퍼)의 표면으로부터 변성된 무기 오염물이 제거된다. After or simultaneously with the modification of the inorganic contaminants on the semiconductor sample by the denaturant, the SCF moves through valve 36 and
변성된 무기 오염물 및 CO2는 제거되며 감압 밸브(18)를 통과하여 무기 오염물이 용기(20) 내에 침전된다. 그 후, CO2 가스는 펌프(24)에 의해 도관(26)을 통해 가스통(28)으로 재순환된다. 무기 오염물은 도관(22)을 통해 제거되게 된다.The denatured inorganic contaminants and CO 2 are removed and passed through a
본 발명의 한 실시예는 전도성, 반도전성 또는 절연성 층의 상부 단층(top monolayer)으로부터 무기 오염물(양호하게는, 금속)을 제거하는 방법이다. "상부 단층"은 일반적으로 층의 상부(5)를 지칭하며, 그 층은 일반적으로 산화물(자연히 존재하는 산화물 층; native oxide layer)로 구성된다.One embodiment of the present invention is a method of removing inorganic contaminants (preferably metal) from a top monolayer of a conductive, semiconductive or insulating layer. "Upper monolayer" generally refers to the
일반적으로, 본 발명의 실시예는 기판 상에 성장된 자연히 존재하는 산화물의 표면 또는 기판 표면으로부터 금속을 포함한 무기 오염물을 초임계 유체(양호하게는, 초임계 CO2) 내의 용매제에 의해 나중에 제거하기 위하여, 그 용매제에 대하여 용해도가 보다 높은 다른 별도의 물질로 화학 변환시킴으로써 제거하는 방법이다. 특히, 본 발명의 방법은 양호하게는, 변환제와 무기 오염물을 반응시켜 그 변환된 무기 오염물 생성물을 용매(양호하게는, 완전 또는 부분적으로 CO2와 같은 초임계 유체 내에 포함되어 있는 용매)에 의해 제거하는 단계를 포함한다. 변환제는 산(양호하게는, KCN, HF, HCl 또는 KI), 염기(양호하게는, NH4OH, KOH 또는 NF3), 킬레이트 및/또는 리간드제(양호하게는, 디베타케톤) 또는 할로겐 함유제(양호하게는, CO, NH3, NO, COS, NH4OH, 물 또는 H2O2)일 수도 있다. 변환제는 증기 노출, 플라즈마 노출에 의해 또는 초임계 유체(양호하게는 CO2) 내의 변환제를 배합하여 이 혼합물에 웨이퍼를 노출시킴으로써 반도체 웨이퍼에 도입될 수도 있다. 용매제는 극성 가스(양호하게는, CO, COS, NO, NH3 또는 NF3), 비극성 가스(양호하게는, N2, H2, O2 또는 F2), 극성 SCF(양호하게는, NO), 비극성 SCF(양호하게는, CO2), 극성 물질(양호하게는, 물, 에탄올, 메탄올, 아세톤 또는 글리콜), 비극성 물질(양호하게는, 테트라하이드로퓨안(tetrahydrofuan) 또는 디메틸포르아미드), 계면 활성제, 세정제, 또는 양성 물질(양호하게는, 소듐 도데실 설파이트, 4가 암모늄염 또는 양이온, 음이온, 무이온 또는 양성 이온 계면 활성제) 또는 킬레이트제(양호하게는, 베타디케톤, 플루오르화되거나 플루오르화되지 않은 크라운 에테르로 이루어진 그룹에서 선택된다.In general, embodiments of the present invention later remove inorganic contaminants, including metals, from the surface of naturally occurring oxides or substrates grown on a substrate by solvent in a supercritical fluid (preferably, supercritical CO 2 ). In order to do this, it is a method of removing by chemically converting into another separate substance having higher solubility with respect to the solvent. In particular, the process of the present invention preferably reacts the converter with an inorganic contaminant to convert the converted inorganic contaminant product into a solvent (preferably, a solvent which is contained, completely or partially, in a supercritical fluid such as CO 2 ). Removing by. The converting agent may be an acid (preferably KCN, HF, HCl or KI), a base (preferably NH 4 OH, KOH or NF 3 ), a chelating and / or ligand (preferably dibetaketone) or Halogen-containing agents (preferably CO, NH 3 , NO, COS, NH 4 OH, water or H 2 O 2 ). The converting agent may be introduced to the semiconductor wafer by vapor exposure, plasma exposure or by combining the converting agent in a supercritical fluid (preferably CO 2 ) to expose the wafer to this mixture. Solvents are polar gases (preferably CO, COS, NO, NH 3 or NF 3 ), nonpolar gases (preferably N 2 , H 2 , O 2 or F 2 ), polar SCF (preferably, NO), nonpolar SCF (preferably CO 2 ), polar substance (preferably water, ethanol, methanol, acetone or glycol), nonpolar substance (preferably tetrahydrofuan or dimethylformamide) , Surfactants, cleaners, or amphoterics (preferably sodium dodecyl sulfite, tetravalent ammonium salts or cations, anions, nonionics or zwitterionic surfactants) or chelating agents (preferably betadiketones, fluorinated) Or a non-fluorinated crown ether.
본 발명의 특정 실시예가 본 명세서에서 기술되었지만, 본 발명의 범위를 제한하는 것으로 해석되지는 않는다. 본 기술 분야의 숙련자라면 본 명세서의 방법으로부터 본 발명의 많은 실시예들을 분명히 알 수 있을 것이다. 본 발명의 범위는 첨부된 특허 청구 범위에 의해서만 제한된다.Although specific embodiments of the invention have been described herein, they are not to be construed as limiting the scope of the invention. Those skilled in the art will clearly see many embodiments of the present invention from the methods herein. It is intended that the scope of the invention only be limited by the appended claims.
도 1은 본 발명의 실시예에 따른 예시적 세정 시스템의 개략도.1 is a schematic diagram of an exemplary cleaning system according to an embodiment of the present invention.
<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>
10 : 세정 시스템10: cleaning system
12 : 변성제12: denaturant
14 : 용매제14: solvent
16 : 세정용 샘플 용기16: sample container for cleaning
24 : 펌프24: pump
28 : 가스통28: gas cylinder
34 : 초임계 유체 가압 장치34: supercritical fluid pressurization device
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2281196P | 1996-07-25 | 1996-07-25 | |
| US60/022,811 | 1996-07-25 |
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| KR980012049A KR980012049A (en) | 1998-04-30 |
| KR100478865B1 true KR100478865B1 (en) | 2005-05-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970034640A KR100478865B1 (en) | 1996-07-25 | 1997-07-24 | Method of removing inorganic contamination by chemical derivitization and extraction |
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| US (1) | US5868856A (en) |
| EP (1) | EP0829312B1 (en) |
| JP (1) | JPH1099806A (en) |
| KR (1) | KR100478865B1 (en) |
| DE (1) | DE69722542T2 (en) |
| TW (1) | TW399226B (en) |
Families Citing this family (86)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08330266A (en) * | 1995-05-31 | 1996-12-13 | Texas Instr Inc <Ti> | Method of cleansing and processing surface of semiconductor device or the like |
| US6306564B1 (en) | 1997-05-27 | 2001-10-23 | Tokyo Electron Limited | Removal of resist or residue from semiconductors using supercritical carbon dioxide |
| US6500605B1 (en) | 1997-05-27 | 2002-12-31 | Tokyo Electron Limited | Removal of photoresist and residue from substrate using supercritical carbon dioxide process |
| AU3360399A (en) | 1998-03-30 | 1999-10-18 | Leisa B. Davenhall | Composition and method for removing photoresist materials from electronic components |
| US6846789B2 (en) * | 1998-03-30 | 2005-01-25 | The Regents Of The University Of California | Composition and method for removing photoresist materials from electronic components |
| US6187911B1 (en) * | 1998-05-08 | 2001-02-13 | Idaho Research Foundation, Inc. | Method for separating metal chelates from other materials based on solubilities in supercritical fluids |
| US6277753B1 (en) * | 1998-09-28 | 2001-08-21 | Supercritical Systems Inc. | Removal of CMP residue from semiconductors using supercritical carbon dioxide process |
| US7044143B2 (en) * | 1999-05-14 | 2006-05-16 | Micell Technologies, Inc. | Detergent injection systems and methods for carbon dioxide microelectronic substrate processing systems |
| US7097715B1 (en) * | 2000-10-11 | 2006-08-29 | R. R. Street Co. Inc. | Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent |
| US6558432B2 (en) * | 1999-10-15 | 2003-05-06 | R. R. Street & Co., Inc. | Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent |
| US6355072B1 (en) | 1999-10-15 | 2002-03-12 | R.R. Street & Co. Inc. | Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent |
| US6755871B2 (en) * | 1999-10-15 | 2004-06-29 | R.R. Street & Co. Inc. | Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent |
| US6748960B1 (en) * | 1999-11-02 | 2004-06-15 | Tokyo Electron Limited | Apparatus for supercritical processing of multiple workpieces |
| AU2001255656A1 (en) * | 2000-04-25 | 2001-11-07 | Tokyo Electron Limited | Method of depositing metal film and metal deposition cluster tool including supercritical drying/cleaning module |
| KR100750018B1 (en) * | 2000-07-26 | 2007-08-16 | 동경 엘렉트론 주식회사 | High pressure processing chamber for semiconductor substrate |
| AU2001279136A1 (en) * | 2000-07-31 | 2002-02-13 | The Deflex Corporation | Near critical and supercritical ozone substrate treatment and apparatus for same |
| JP2002237481A (en) * | 2001-02-09 | 2002-08-23 | Kobe Steel Ltd | Method of cleaning microscopic structure |
| US6613157B2 (en) | 2001-02-15 | 2003-09-02 | Micell Technologies, Inc. | Methods for removing particles from microelectronic structures |
| US6562146B1 (en) * | 2001-02-15 | 2003-05-13 | Micell Technologies, Inc. | Processes for cleaning and drying microelectronic structures using liquid or supercritical carbon dioxide |
| US6596093B2 (en) | 2001-02-15 | 2003-07-22 | Micell Technologies, Inc. | Methods for cleaning microelectronic structures with cyclical phase modulation |
| US6641678B2 (en) | 2001-02-15 | 2003-11-04 | Micell Technologies, Inc. | Methods for cleaning microelectronic structures with aqueous carbon dioxide systems |
| US6905555B2 (en) | 2001-02-15 | 2005-06-14 | Micell Technologies, Inc. | Methods for transferring supercritical fluids in microelectronic and other industrial processes |
| US6602351B2 (en) | 2001-02-15 | 2003-08-05 | Micell Technologies, Inc. | Methods for the control of contaminants following carbon dioxide cleaning of microelectronic structures |
| US20020189543A1 (en) * | 2001-04-10 | 2002-12-19 | Biberger Maximilian A. | High pressure processing chamber for semiconductor substrate including flow enhancing features |
| US6561220B2 (en) * | 2001-04-23 | 2003-05-13 | International Business Machines, Corp. | Apparatus and method for increasing throughput in fluid processing |
| US6946055B2 (en) * | 2001-08-22 | 2005-09-20 | International Business Machines Corporation | Method for recovering an organic solvent from a waste stream containing supercritical CO2 |
| US6619304B2 (en) | 2001-09-13 | 2003-09-16 | Micell Technologies, Inc. | Pressure chamber assembly including non-mechanical drive means |
| US6706641B2 (en) | 2001-09-13 | 2004-03-16 | Micell Technologies, Inc. | Spray member and method for using the same |
| US6782900B2 (en) | 2001-09-13 | 2004-08-31 | Micell Technologies, Inc. | Methods and apparatus for cleaning and/or treating a substrate using CO2 |
| US6666928B2 (en) | 2001-09-13 | 2003-12-23 | Micell Technologies, Inc. | Methods and apparatus for holding a substrate in a pressure chamber |
| US6763840B2 (en) | 2001-09-14 | 2004-07-20 | Micell Technologies, Inc. | Method and apparatus for cleaning substrates using liquid carbon dioxide |
| PL370305A1 (en) * | 2001-11-06 | 2005-05-16 | The Procter & Gamble Company | Multi-motion toothbrush |
| JP2003224099A (en) * | 2002-01-30 | 2003-08-08 | Sony Corp | Surface treatment method |
| JP2006508521A (en) * | 2002-02-15 | 2006-03-09 | 東京エレクトロン株式会社 | Drying of resist using solvent bath and supercritical CO2 |
| US6924086B1 (en) * | 2002-02-15 | 2005-08-02 | Tokyo Electron Limited | Developing photoresist with supercritical fluid and developer |
| US6953654B2 (en) | 2002-03-14 | 2005-10-11 | Tokyo Electron Limited | Process and apparatus for removing a contaminant from a substrate |
| US7128840B2 (en) | 2002-03-26 | 2006-10-31 | Idaho Research Foundation, Inc. | Ultrasound enhanced process for extracting metal species in supercritical fluids |
| US6764552B1 (en) | 2002-04-18 | 2004-07-20 | Novellus Systems, Inc. | Supercritical solutions for cleaning photoresist and post-etch residue from low-k materials |
| US20030217764A1 (en) * | 2002-05-23 | 2003-11-27 | Kaoru Masuda | Process and composition for removing residues from the microstructure of an object |
| US6846380B2 (en) * | 2002-06-13 | 2005-01-25 | The Boc Group, Inc. | Substrate processing apparatus and related systems and methods |
| US20040050406A1 (en) * | 2002-07-17 | 2004-03-18 | Akshey Sehgal | Compositions and method for removing photoresist and/or resist residue at pressures ranging from ambient to supercritical |
| US20040011386A1 (en) * | 2002-07-17 | 2004-01-22 | Scp Global Technologies Inc. | Composition and method for removing photoresist and/or resist residue using supercritical fluids |
| US6905556B1 (en) | 2002-07-23 | 2005-06-14 | Novellus Systems, Inc. | Method and apparatus for using surfactants in supercritical fluid processing of wafers |
| US7282099B2 (en) * | 2002-09-24 | 2007-10-16 | Air Products And Chemicals, Inc. | Dense phase processing fluids for microelectronic component manufacture |
| US20080004194A1 (en) * | 2002-09-24 | 2008-01-03 | Air Products And Chemicals, Inc. | Processing of semiconductor components with dense processing fluids |
| US7267727B2 (en) * | 2002-09-24 | 2007-09-11 | Air Products And Chemicals, Inc. | Processing of semiconductor components with dense processing fluids and ultrasonic energy |
| US20080000505A1 (en) * | 2002-09-24 | 2008-01-03 | Air Products And Chemicals, Inc. | Processing of semiconductor components with dense processing fluids |
| US6953041B2 (en) * | 2002-10-09 | 2005-10-11 | Micell Technologies, Inc. | Compositions of transition metal species in dense phase carbon dioxide and methods of use thereof |
| US20040175948A1 (en) * | 2002-10-10 | 2004-09-09 | The University Of North Carolina At Chapel Hill | Metal chelation in carbon dioxide |
| US7223352B2 (en) * | 2002-10-31 | 2007-05-29 | Advanced Technology Materials, Inc. | Supercritical carbon dioxide/chemical formulation for ashed and unashed aluminum post-etch residue removal |
| US7011716B2 (en) * | 2003-04-29 | 2006-03-14 | Advanced Technology Materials, Inc. | Compositions and methods for drying patterned wafers during manufacture of integrated circuitry products |
| US7485611B2 (en) * | 2002-10-31 | 2009-02-03 | Advanced Technology Materials, Inc. | Supercritical fluid-based cleaning compositions and methods |
| JP2004158534A (en) * | 2002-11-05 | 2004-06-03 | Kobe Steel Ltd | Method for cleaning microscopic structure |
| US6997197B2 (en) * | 2002-12-13 | 2006-02-14 | International Business Machines Corporation | Apparatus and method for rapid thermal control of a workpiece in liquid or dense phase fluid |
| US20040112409A1 (en) * | 2002-12-16 | 2004-06-17 | Supercritical Sysems, Inc. | Fluoride in supercritical fluid for photoresist and residue removal |
| US20040154647A1 (en) * | 2003-02-07 | 2004-08-12 | Supercritical Systems, Inc. | Method and apparatus of utilizing a coating for enhanced holding of a semiconductor substrate during high pressure processing |
| US6875709B2 (en) * | 2003-03-07 | 2005-04-05 | Taiwan Semiconductor Manufacturing Comapny, Ltd. | Application of a supercritical CO2 system for curing low k dielectric materials |
| US20040198066A1 (en) * | 2003-03-21 | 2004-10-07 | Applied Materials, Inc. | Using supercritical fluids and/or dense fluids in semiconductor applications |
| US20050029492A1 (en) * | 2003-08-05 | 2005-02-10 | Hoshang Subawalla | Processing of semiconductor substrates with dense fluids comprising acetylenic diols and/or alcohols |
| EP1673802A1 (en) * | 2003-10-14 | 2006-06-28 | EKC Technology, INC. | REMOVAL OF POST ETCH RESIDUES AND COPPER CONTAMINATION FROM LOW-K DIELECTRICS USING SUPERCRITICAL CO sb 2 /sb WITH DIKETONE ADDITIVES |
| US7741012B1 (en) | 2004-03-01 | 2010-06-22 | Advanced Micro Devices, Inc. | Method for removal of immersion lithography medium in immersion lithography processes |
| US20050241672A1 (en) * | 2004-04-28 | 2005-11-03 | Texas Instruments Incorporated | Extraction of impurities in a semiconductor process with a supercritical fluid |
| US7250374B2 (en) * | 2004-06-30 | 2007-07-31 | Tokyo Electron Limited | System and method for processing a substrate using supercritical carbon dioxide processing |
| US7195676B2 (en) * | 2004-07-13 | 2007-03-27 | Air Products And Chemicals, Inc. | Method for removal of flux and other residue in dense fluid systems |
| US7307019B2 (en) * | 2004-09-29 | 2007-12-11 | Tokyo Electron Limited | Method for supercritical carbon dioxide processing of fluoro-carbon films |
| US20060065288A1 (en) * | 2004-09-30 | 2006-03-30 | Darko Babic | Supercritical fluid processing system having a coating on internal members and a method of using |
| US20060081273A1 (en) * | 2004-10-20 | 2006-04-20 | Mcdermott Wayne T | Dense fluid compositions and processes using same for article treatment and residue removal |
| US7491036B2 (en) * | 2004-11-12 | 2009-02-17 | Tokyo Electron Limited | Method and system for cooling a pump |
| US20060102208A1 (en) * | 2004-11-12 | 2006-05-18 | Tokyo Electron Limited | System for removing a residue from a substrate using supercritical carbon dioxide processing |
| US20060102590A1 (en) * | 2004-11-12 | 2006-05-18 | Tokyo Electron Limited | Method for treating a substrate with a high pressure fluid using a preoxide-based process chemistry |
| US20060102204A1 (en) * | 2004-11-12 | 2006-05-18 | Tokyo Electron Limited | Method for removing a residue from a substrate using supercritical carbon dioxide processing |
| US7140393B2 (en) * | 2004-12-22 | 2006-11-28 | Tokyo Electron Limited | Non-contact shuttle valve for flow diversion in high pressure systems |
| US20060135047A1 (en) * | 2004-12-22 | 2006-06-22 | Alexei Sheydayi | Method and apparatus for clamping a substrate in a high pressure processing system |
| US7434590B2 (en) * | 2004-12-22 | 2008-10-14 | Tokyo Electron Limited | Method and apparatus for clamping a substrate in a high pressure processing system |
| US7291565B2 (en) * | 2005-02-15 | 2007-11-06 | Tokyo Electron Limited | Method and system for treating a substrate with a high pressure fluid using fluorosilicic acid |
| US20060180174A1 (en) * | 2005-02-15 | 2006-08-17 | Tokyo Electron Limited | Method and system for treating a substrate with a high pressure fluid using a peroxide-based process chemistry in conjunction with an initiator |
| US7435447B2 (en) * | 2005-02-15 | 2008-10-14 | Tokyo Electron Limited | Method and system for determining flow conditions in a high pressure processing system |
| US20060180572A1 (en) * | 2005-02-15 | 2006-08-17 | Tokyo Electron Limited | Removal of post etch residue for a substrate with open metal surfaces |
| US20060255012A1 (en) * | 2005-05-10 | 2006-11-16 | Gunilla Jacobson | Removal of particles from substrate surfaces using supercritical processing |
| US7789971B2 (en) * | 2005-05-13 | 2010-09-07 | Tokyo Electron Limited | Treatment of substrate using functionalizing agent in supercritical carbon dioxide |
| US7524383B2 (en) * | 2005-05-25 | 2009-04-28 | Tokyo Electron Limited | Method and system for passivating a processing chamber |
| US20070012337A1 (en) * | 2005-07-15 | 2007-01-18 | Tokyo Electron Limited | In-line metrology for supercritical fluid processing |
| JP4963815B2 (en) * | 2005-09-07 | 2012-06-27 | ソニー株式会社 | Cleaning method and semiconductor device manufacturing method |
| JP2007251081A (en) * | 2006-03-20 | 2007-09-27 | Dainippon Screen Mfg Co Ltd | Substrate processing method |
| US10144874B2 (en) * | 2013-03-15 | 2018-12-04 | Terrapower, Llc | Method and system for performing thermochemical conversion of a carbonaceous feedstock to a reaction product |
| CN110899248A (en) * | 2019-06-21 | 2020-03-24 | 杭州杭氧股份有限公司 | System and method for cleaning ultrahigh-purity gas steel cylinders in batch by using supercritical fluid |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749440A (en) * | 1985-08-28 | 1988-06-07 | Fsi Corporation | Gaseous process and apparatus for removing films from substrates |
| US5105556A (en) * | 1987-08-12 | 1992-04-21 | Hitachi, Ltd. | Vapor washing process and apparatus |
| JPH01204427A (en) * | 1988-02-10 | 1989-08-17 | Hitachi Ltd | Semiconductor device |
| US5068040A (en) * | 1989-04-03 | 1991-11-26 | Hughes Aircraft Company | Dense phase gas photochemical process for substrate treatment |
| US4923828A (en) * | 1989-07-07 | 1990-05-08 | Eastman Kodak Company | Gaseous cleaning method for silicon devices |
| DE69231971T2 (en) * | 1991-01-24 | 2002-04-04 | Wako Pure Chem Ind Ltd | Solutions for surface treatment of semiconductors |
| US5356538A (en) * | 1991-06-12 | 1994-10-18 | Idaho Research Foundation, Inc. | Supercritical fluid extraction |
| CA2125965A1 (en) * | 1991-12-18 | 1993-06-24 | Michelle A. De Crosta | Method for removing residual additives from elastomeric articles |
| US5352327A (en) * | 1992-07-10 | 1994-10-04 | Harris Corporation | Reduced temperature suppression of volatilization of photoexcited halogen reaction products from surface of silicon wafer |
| US5316591A (en) * | 1992-08-10 | 1994-05-31 | Hughes Aircraft Company | Cleaning by cavitation in liquefied gas |
| US5261965A (en) * | 1992-08-28 | 1993-11-16 | Texas Instruments Incorporated | Semiconductor wafer cleaning using condensed-phase processing |
| JP3338134B2 (en) * | 1993-08-02 | 2002-10-28 | 株式会社東芝 | Semiconductor wafer processing method |
| US5377705A (en) * | 1993-09-16 | 1995-01-03 | Autoclave Engineers, Inc. | Precision cleaning system |
| US5656097A (en) * | 1993-10-20 | 1997-08-12 | Verteq, Inc. | Semiconductor wafer cleaning system |
| TW274630B (en) * | 1994-01-28 | 1996-04-21 | Wako Zunyaku Kogyo Kk | |
| EP0681317B1 (en) * | 1994-04-08 | 2001-10-17 | Texas Instruments Incorporated | Method for cleaning semiconductor wafers using liquefied gases |
| US5637151A (en) * | 1994-06-27 | 1997-06-10 | Siemens Components, Inc. | Method for reducing metal contamination of silicon wafers during semiconductor manufacturing |
| US5522938A (en) * | 1994-08-08 | 1996-06-04 | Texas Instruments Incorporated | Particle removal in supercritical liquids using single frequency acoustic waves |
| US5501761A (en) * | 1994-10-18 | 1996-03-26 | At&T Corp. | Method for stripping conformal coatings from circuit boards |
| US5681398A (en) * | 1995-03-17 | 1997-10-28 | Purex Co., Ltd. | Silicone wafer cleaning method |
| JPH08264500A (en) * | 1995-03-27 | 1996-10-11 | Sony Corp | Cleaning of substrate |
| US5679169A (en) * | 1995-12-19 | 1997-10-21 | Micron Technology, Inc. | Method for post chemical-mechanical planarization cleaning of semiconductor wafers |
-
1997
- 1997-07-23 US US08/898,936 patent/US5868856A/en not_active Expired - Lifetime
- 1997-07-24 KR KR1019970034640A patent/KR100478865B1/en not_active IP Right Cessation
- 1997-07-25 EP EP97305628A patent/EP0829312B1/en not_active Expired - Lifetime
- 1997-07-25 DE DE69722542T patent/DE69722542T2/en not_active Expired - Lifetime
- 1997-07-25 JP JP9199998A patent/JPH1099806A/en active Pending
- 1997-11-21 TW TW086110690A patent/TW399226B/en not_active IP Right Cessation
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| Publication number | Publication date |
|---|---|
| EP0829312A2 (en) | 1998-03-18 |
| EP0829312A3 (en) | 1999-09-15 |
| DE69722542T2 (en) | 2004-05-13 |
| TW399226B (en) | 2000-07-21 |
| US5868856A (en) | 1999-02-09 |
| KR980012049A (en) | 1998-04-30 |
| EP0829312B1 (en) | 2003-06-04 |
| DE69722542D1 (en) | 2003-07-10 |
| JPH1099806A (en) | 1998-04-21 |
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